WO2017076744A1 - Continuous method for reactions with fine-particulate alkali metal dispersions - Google Patents
Continuous method for reactions with fine-particulate alkali metal dispersions Download PDFInfo
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- WO2017076744A1 WO2017076744A1 PCT/EP2016/075956 EP2016075956W WO2017076744A1 WO 2017076744 A1 WO2017076744 A1 WO 2017076744A1 EP 2016075956 W EP2016075956 W EP 2016075956W WO 2017076744 A1 WO2017076744 A1 WO 2017076744A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/70—Spray-mixers, e.g. for mixing intersecting sheets of material
- B01F25/74—Spray-mixers, e.g. for mixing intersecting sheets of material with rotating parts, e.g. discs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00752—Feeding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/0072—Organic compounds
Definitions
- the present invention relates to a continuous process in which, especially on a spinning disk reactor (SDR), fine alkali metal dispersions are generated in organic solvents and used for coupling organic esters and halides as well as organohalosilanes.
- SDR spinning disk reactor
- Alkali metals, and especially sodium have long been established as reagents in organic chemistry, for example, for the preparation of alkoxides, for the Darzens glycidester condensation, for Birch reduction for the conversion of aromatic to aliphatic compounds, or for the acyloin condensation of esters ⁇ -Hydroxycarbonyl Compounds (K. Rühlmann Synthesis (1971), (1971 (5), 236-253).) Especially the latter reaction is of importance in organic chemistry for the intramolecular cyclization of dicarboxylic acid esters to middle and large ring systems.
- Wurtz coupling Another major field of application for elemental alkali metals is the Wurtz coupling, or Wurtz's synthesis, discovered in 1854 by the French chemist Adolphe Wurtz, which initially served primarily to synthesize (cyclo) alkanes starting from haloalkanes.
- Wurtz'schen synthesis are cycloalkanes of the ring size of three to accessible to six carbon atoms.
- the Wurtz coupling is also the major route for producing ⁇ - ⁇ -conjugated silicon polymers via the polycondensation of halosilanes in aprotic organic solvents (RD Miller, J. Michl Chemical Reviews (1989), 89 (6), 1359-1410).
- SDRs are state of the art for the epoxidation of substituted cyclohexanones EP 1 20 6460 B1, reactions of carboxy acids and esters WO 2002/018328 Al, the preparation of nanoparticles US Pat. No. 8,870,998 B2, for the hydrogenation of nitrile rubber in solution EP 1 862 477 Bl, for heterogeneously catalyzed reactions EP 1 152 823 B2, and for carrying out free-radical emulsion polymerizations US Pat. No. 7,683,142 B2.
- the present invention is based on the object of providing a continuous process for carrying out chemical reactions with liquid finely divided alkali metal dispersions in inert solvents, which is not limited by the described problems of the semibatch procedure.
- PFRs plug flow reactors
- CSTR continuous stirred tank reactors
- MRT microreaction technology
- SDR spinning disk reactor
- the essential problems of a semibatch process for carrying out reactions with finely divided alkali metal dispersions can be eliminated by a continuous procedure:
- a continuous reaction process only small amounts of hazardous substances per unit time are combined and ideally mixed efficiently here. If a strongly exothermic reaction is handled, the resulting heat can be well dissipated by a high surface-to-volume ratio, resulting in a homogeneous temperature profile in the reaction mixture. All this leads according to the invention to a significant improvement in the safety aspect of such reactions, as well as to a significantly improved reproducibility of the product quality in the stationary state of such a continuous process.
- the present invention finds particular application for the Wurtz coupling of halogen compounds, as well as for the Acyloinkon- condensation of esters.
- the liquid two-phase system present in each case before the reaction or the concentrated salt dispersion produced in the Wurtz coupling results in continuously operated SDR due to the high shear forces in this dynamic system not fouling and blocking.
- Fig. 1 shows an exemplary flow chart for the present invention: the reference numeral 1 stands for a dosing container with liquid alkali metal or alkali metal mixture / alloy;
- the reference numeral 2 stands for a metering container of the reactant or a reactant mixture;
- the reference numeral 3 stands for a dosing of the solvent or a solvent mixture;
- the reference numeral 4 stands for a spinning disk reactor (SDR);
- the reference numeral 5 stands for an optional residence time unit (for example stirred tank, stirred tank cascade, heat exchanger);
- the reference numeral 6 stands for a collecting container of the product mixture;
- the reference numeral 7 stands for a collecting container of the by-product mixture.
- the rotary disk reactor could be developed as a suitable technology for carrying out reactions with liquid alkali metal dispersions in inert organic solvents, in particular the Wurtz coupling of halogen compounds and the acyclocondensation, to form solid precipitates.
- This reactor type was developed for process intensification to optimize especially heat transport (heating, cooling, heat exchange) and mass transfer processes (mixing, dispersing):
- the technology is based on one or more disks, which are mounted horizontally on a rotating axis, which is a electric motor is driven. A liquid applied to the surface of this disc is passed through the acting centrifugal acceleration to the edge of the plate or thrown over.
- the use described in this invention takes place in a liquid medium which consists of an inert solvent or solvent mixture and the reactants dissolved therein (for example haloalkanes, halosilanes, esters).
- a liquid medium which consists of an inert solvent or solvent mixture and the reactants dissolved therein (for example haloalkanes, halosilanes, esters).
- the reactants dissolved therein for example haloalkanes, halosilanes, esters.
- the alkali metal or the alkali metal mixture or alloy used in a molten state in order to finely disperse it in the reaction medium.
- the alkali metal or the alkali metal mixture or alloy, the reactants and solvents are each metered separately into the reactor.
- reaction of the alkali metal or the alkali metal mixture or alloy with the reactants forms an alkali metal salt which is insoluble in the reaction mixture and, depending on the type of reaction, a coupling product which is soluble or else insoluble in the liquid medium. It is a continuous multiphase reaction in which the reactive phases are liquid and one or more reaction products precipitates as a solid precipitate.
- alkali metals for the preparation of the alkali metal dispersion are in principle all alkali metals, their mixtures and / or alloys suitable. Preference is given to alkali metals or mixtures and / or alloys thereof, whose melting point is in the range between -20 and 190 ° C. Particularly preferred are lithium, sodium and potassium and their mixtures and alloys, since they are technically easily accessible and melt in a temperature range which is technically easy to handle.
- inert solvents it is possible to use all industrially customary aprotic organic solvents in which the reactants (for example halogen compounds of the elements of main group IV or organic esters) are soluble and which do not react with the alkali metal or alkali metal mixture or alloy used.
- Hydrocarbons such as benzene, toluene, xylene and aliphatic hydrocarbons are preferably used.
- Hydrogens, and ethers such as dioxane, anisole and THF.
- the inert solvent may also be a mixture of said solvents, e.g. Example of a hydrocarbon and an ether, so for example toluene and THF.
- the alkali metal salt formed in the reaction is not soluble in the solvent used and can be separated by filtration of the precipitate.
- Suitable reactants are various substances:
- the process according to the invention makes it possible to react all substrates customary for the Wurtz coupling, such as mono-, di-, tri- and polyfunctional alkyl and aryl halides and mixtures thereof, and also mono-, di-, tri- and polyfunctional haloorganosilanes and mixtures thereof .
- halogens in the halogen compounds fluorine, chlorine, bromine and iodine can be used, preferably chlorine, bromine and iodine, more preferably chlorine and bromine are used.
- the invention is suitable for the preparation of polysilanes and polycarbosilanes from halogenated organosilane building blocks which are not polysilanes.
- the halogenated organosilane building blocks are defined by having less than 5 silicon atoms, preferably at most 3 silicon atoms, more preferably at most 2 silicon atoms, and most preferably only one silicon atom.
- the amount of the solvent, the alkali metal and the reactants is to be chosen so that the reaction medium remains fluid even after formation of solid alkali metal halides and possibly the insoluble products, so that fouling and blocking the SDR remain minimized.
- from 5 to 99% by weight of solvent based on the total reaction mixture is used, preferably from 50 to 97% by weight, more preferably from 70 to 95% by weight of solvent fraction.
- the ratio of the alkali metals used or their mixtures and / or alloys to the reactants is chosen so that as complete a conversion as possible is achieved.
- the most stoichiometric possible use is preferred.
- For the preparation of polymeric coupling products typically requires an excess of the alkali metal over the halide, preferably an excess of up to 20 wt.%, More preferably an excess of up to 10 wt.%, Most preferably an excess of up to 5 wt %.
- the process described in this invention can be carried out in a wide temperature range.
- the temperature range is limited by being a multi-phase process with two liquids, more specifically the molten alkali metal or the molten alkali metal mixture or alloy and the reaction medium of solvent and reactants. This results in the lower limit for the temperature range, the melting temperature of the alkali metal or the alkali metal alloy / Mixed.
- the upper limit results from the boiling range of the reaction mixture and the technical design of the SDR.
- the reaction is carried out in a range between 50 and 200 ° C, more preferably between 100 and 115 ° C.
- the rotational speed of the rotating disk of the SDR must be chosen so that an optimal dispersion of the liquid alkali metal or the alkali metal mixture / alloy in the solvent is achieved.
- a further advantage of the present invention is the high surface-to-volume ratio of the reaction mixture and the efficient mixing thereof, which makes possible an efficient removal of the amount of heat generated in the exothermic reaction.
- This results in a short residence time of the reaction mixture in the SDR and thus a short total process time while reducing the risk potential of the reaction.
- the resulting high space-time yield makes the described method economically very interesting compared to established semibatch methods.
- the residence time of the reaction mixture in the SDR is ⁇ 10 min, more preferably ⁇ 5 min. During this time, most of the exotherm of the reaction is released and removed.
- the reaction product may be separated from the reaction mixture by any suitable method known to those skilled in the art and optionally purified. For example, if the product is soluble in the reaction medium, first the solid alkali metal salt precipitate is separated by filtration with any remaining alkali metal. Then, the product is obtained, for example, by fractional distillation or distilling off the solvent. If the product is insoluble in the reaction medium, it can be separated by filtration together with the solid alkali metal salt precipitate and optionally residual alkali metal by filtration. Unreacted alkali metal is optionally deactivated with protic solvents and the alkali metal salts are extracted with water. These are examples.
- the dichlorophenylmethylsilane was metered into this suspension over a period of about 30 minutes. The onset of the reaction could be observed by an increase in temperature, and an intense violet coloration of the reaction mixture.
- the metering rate was to be chosen so that the Dichlorphenylmethylsilan was added evenly over the metering time and at the same time the reaction temperature always in the temperature window of 102 - 106 ° C remained.
- the reaction mixture was stirred for 2 h at 102 ° C after the end of the dosage. After cooling to room temperature, the resulting suspension was filtered under protective gas over a ceramic frit (G4). The filtrate was concentrated by distilling off the solvent mixture in vacuo to obtain the soluble portion of the formed poly (methylphenylsilane).
- the polymer was purified by means of ⁇ -NMR- 13 C NMR, 29 Si NMR spectroscopy (each in C 6 D 6 ) and gel permeation chromatography (in THF with light scattering detector).
- the SDR was set to a rotational speed of 1000 or 2500 rpm, a heating oil temperature of 100 or 105 ° C and initially a xylene flow of 6.5 kg / h.
- the sodium dosage was started.
- the metered addition of the dichloromethylphenylsilane was started.
- the mass ratio of dichloromethylphenylsilane to sodium was constant at 5/1 in all experiments.
- the onset of the reaction was immediately evident from the temperature rise on the first and second plates of the reactor. Later, the deep violet-colored reaction mixture exited into the collection container. Dosing rates and oil temperatures were varied as shown in the table.
- the product was filtered off under nitrogen over a G4-F ceramic tip and the solvent was completely distilled off under vacuum.
- the polymer was prepared by ⁇ NMR, 13 C NMR, 29 Si NMR spectroscopy (in each case in C 6 D 6 ) and gel permeation chromatography (in THF with light scattering detector).
- the sodium dosage was started at 2 g / min.
- the temperature in the reactor settled at 122 ° C.
- the monomer feed was started at 10 g / min.
- the beginning of the reaction was immediately recognizable by the temperature increase in the reactor to 129 ° C on the first platinum. te. A little later, the deep violet-colored reaction mixture exited into the collecting container.
- the product was filtered off under nitrogen and the solvent was distilled off.
- the polymer was characterized by ⁇ -NMR, 13 C-NMR, 29 Si-NMR spectroscopy (each in C 6 D 6 ) and gel permeation chromatography (in THF with light scattering detector).
- the sodium dosage was started at 1.0 g / min.
- the temperature in the reactor settled at 122 ° C.
- the dosage of 1,6-dibromohexane was started at 4 g / min.
- the onset of the reaction was immediately evident from the temperature rise in the reactor to 127 ° C on the first plate. A little later, the deep violet-colored reaction mixture exited into the collecting container.
- the product was filtered off under nitrogen, the composition of the filtrate analyzed by GC-MS and a turnover of 98.5%.
- the pure product was obtained by fractional distillation of the filtrate in 91% yield and analyzed by 1 H and 13 C NMR spectroscopy.
Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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AU2016349664A AU2016349664B2 (en) | 2015-11-03 | 2016-10-27 | Continuous method for reactions with fine-particulate alkali metal dispersions |
RU2018119678A RU2728775C2 (en) | 2015-11-03 | 2016-10-27 | Continuous method of carrying out reactions with fine dispersions of alkali metals |
JP2018543433A JP6850810B2 (en) | 2015-11-03 | 2016-10-27 | Continuous method for reaction with fine particle alkali metal dispersion |
KR1020187012136A KR102567309B1 (en) | 2015-11-03 | 2016-10-27 | Continuous Reaction Method Using Particulate Alkali Metal Dispersion |
CN201680063034.2A CN108431092B (en) | 2015-11-03 | 2016-10-27 | Continuous process for reacting with particulate alkali metal dispersions |
EP16787873.5A EP3371248A1 (en) | 2015-11-03 | 2016-10-27 | Continuous method for reactions with fine-particulate alkali metal dispersions |
US15/771,768 US10494486B2 (en) | 2015-11-03 | 2016-10-27 | Continuous method for reactions with fine-particulate alkali metal dispersions |
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DE102015221529.6 | 2015-11-03 | ||
DE102015221529.6A DE102015221529A1 (en) | 2015-11-03 | 2015-11-03 | Continuous process for reactions with finely divided alkali metal dispersions |
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EP (1) | EP3371248A1 (en) |
JP (1) | JP6850810B2 (en) |
KR (1) | KR102567309B1 (en) |
CN (1) | CN108431092B (en) |
AU (1) | AU2016349664B2 (en) |
DE (1) | DE102015221529A1 (en) |
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CN109384932A (en) * | 2018-10-29 | 2019-02-26 | 北京瑞思达化工设备有限公司 | A kind of technique of continuous production types of silicon carbide-based ceramics precursor polymethyl silicane |
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2015
- 2015-11-03 DE DE102015221529.6A patent/DE102015221529A1/en active Pending
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2016
- 2016-10-27 EP EP16787873.5A patent/EP3371248A1/en active Pending
- 2016-10-27 US US15/771,768 patent/US10494486B2/en active Active
- 2016-10-27 WO PCT/EP2016/075956 patent/WO2017076744A1/en active Application Filing
- 2016-10-27 AU AU2016349664A patent/AU2016349664B2/en active Active
- 2016-10-27 CN CN201680063034.2A patent/CN108431092B/en active Active
- 2016-10-27 RU RU2018119678A patent/RU2728775C2/en active
- 2016-10-27 KR KR1020187012136A patent/KR102567309B1/en active IP Right Grant
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